Linear polymeric amides and methods of making them



(Un ted S ates Pa e LINEAR POLYMERIC AMlDES AND METHODS OF MAKING THEMSidney-Melamed, Philadelphia, .P a.,;assign'or to Robin 8; Haas Company,Philadelphia, Pa., a corporation of Delaware No Drawing. ApplicationAugust 4,1954 Serial No; 447,890

. 6 clai s. or. 26.0-39.7

ondary basic nitrogen" atorrrsin side chains orib ranch groups and suchatoms are connected to; the linear backbone by alkyleneamido linkageswhich may or may not contain one or'mor e ether oxygen atoms Thecompounds 1 have! numerous uses. Their basic nitrogen atomscarryingtreactive, hydrogen widen their field of utility and providereactive centers adapting/the compounds to be'thermoset' orinsolubilized, such as'by formaldehyde and other reactants, and. also tobe converted into many highly useful derivatives as willbe moreparticularly pointed oufhereinafter. The amide linkagecontributes-towater-solubility whenthe polymers are of water-soluble orwater-dispersible character and tends to reduce hydrophobocity where aWater-insoluble polymer is involved. The amide linkages may also providean additional point of formaldehyde reactivity when a reactive hydrogenis carried on the nitrogen of this linkage. The amide group alsoenhances the resistance of the polymer to the tendency of hard water todeactivate the polymer whenitris of a type having bactericidalproperties. It is possibleithat thisis accomplished by a sequestering orchelatirig action.

It has. been discovered in accordance with the present invention thatthe new'polymers'may be made by the.

aminolysis of a polymeric ester of an--a, 3-un'saturated monocarboxylicacid with certain polyamines, especially in which R is H or CH R is H oran alkyl or hydroxyalkyl group of 1 to 24 carbon atoms, R, is an alkylor hydroxyalkyl group of 1 to 24 carbon atoms, or an aryl, alkaryhoraralkyl group having-'6 to 24 carbon atoms, R is 'an alkyl orhydroxyalkyl group 'of l to-24. carbon atoms or an aryl; alkaryl,.orraralkyl group having-:6 to 24 carbon atoms; n is anvinteger havinga'value of 1 to 2, A is an alkylene group-of 2to 10 carbon atoms,an-alkyleneoxyalkyl group;-of=4 "to 10 carbon: :atoms-lor a (poly:-alkyleneoxy) alkylgroup. of 4 'to:10; carbon atoms, 7

in which HR is defined above is, 1anc allcylene group of l to 10 carbonatoms, R is an alkyl group of 1 was 1 carbon atoms, R is an alkyl groupof l to 18 carbon atoms, and v I H CH: c-

3' g; 0: -'--N NH a, an) in which R is defined above. :These newpolymericcomp'ounds' are solid resinous products having atleastfivemonomeri'cmhits ofr the'type defined having one of the Formulas-91, II,or III.'.t. Gen'- eral ly, thepolymers contain irony-20 to-"20,000monomeric units of which at leastfive contain 'grloups'fhavinga-basicnitrogen atom carryingtreactive' hydrogenii 'The polyrners are oflinear' character in tthe'i sense'zthattheyare not cross-linked althoughtheyamayi contain numerous branches. from the 'linearw'backbonex 1-,Thenlinear bacb bone or chain consistssubstantially;entirelysofdirect'car- ,bon-to-carbon-linkages,there-being nointervening: or interrupting non-carbon: atoms iexcept inthe terminal hnits oi the-polymer,- The; polymers contain primaryorsecdiamines and triamincs, in which the basic nitrogen atoms are ofprimary or secondary character and one only of these nitrogen atoms isaprimary or secondary nitrogen attached exclusively to primary carbonor-isya primary nitrogen attached to a secondarycarbon atom. It fo1-' Ilows from this-that if'theother of'thes'efniti'ogen atoms is primary, itor they must beattachedto, a tertiary carbon, and if secondary, or theymay beattach'ed to (1) a primary'carbon' an'd-a secondary carbon, (2) aprimary carbon and a tertiary carbon, ((3) two secondary carbons,

or (4) two tertiary carbons.

These polyamines react, in eifect, as monoamines in the aminolysis, thefirst-mentioned nitrogen atom being the only one whichbecomes attachedto a carbonyl group of the polymeric ester" to form an amide. The othernitrogen atoms are" apparently. sterically hindered from reactingsimilarly. The polyamines which react infthis I fashion'to'produce'polyamides of linear type have the structure ofone ofthe"Formulas-IV,vgaaa VI followin which formulas, the symbols have, thesamedefinitionsas are given hereinberore; Examples of the diamines are i V as follows:7 t-Butylaminopropylamine j V IsoproPylaminoNQpvhrnine (CH3 2CHNH(CH2 az t-Butylaminoethylamine cng cNmcnp un 2,845,408 Patented July 29,-1958' Isop ropylaminoethylamine 3 zcHNH 2) z z t-Butylaminop entylamine3) a 2) s z Isopropylaminop entylamine 3 zCHNH 2) :s zt-Butylaminodecylamine (CH3)3CNTI(CH2)10NH2 Isopropyl amino decylamine3) ZCHNH 2) io z t-Butylaminoethoxyethoxyethylamine (CH3-CNHC2H4OC2H4OC2H4NHg 2,6-dimethylpiperazine C H; C fir-( 1H EN NH 2-amino- 1 1, 1,4, 4-tetramethylbutylamino) butane (CH3)ZCNHCH2CHNH2CH2CH30 H2 C C a Tris- (hydroxymethyl methylaminopropylamine z a 2 a aBenzyldimethyl) methyl aminodecylamine e 5 2 2 2) NH2 (Benzyldimethyl)methylamino ethoxyethylam'ine (C H CH C (CH NHC H O C H NHw-Hydroxydecyldimethyl) methylaminopropylamine 2)1o 3)2 Z)s z(Heneicosyldimethyl methylaminoethoxyethoxyethylamine 21 43 3 2 H 2 4 22 4 z (Benzyldimethyl) methyl aminohexylamine e s z 3 z 2) s a l-(l-cyclohexylethylamino) -2-amino-prop ane C H CH(CH NHCH CHNH CH(p-Chlorophenyldimethyl) methylaminopropylamine (BIO-C(CHOzNEHOHQ NH:

(p -Nitrophenyldim-ethyl methylaminopropyl amine NmOowmnNmomnNm(p-Methoxyphenyldimethyl)methylaminopropylamine 0113006 (OHQzNEKCHflaNHal,2-diamino-Z-methyl-propane 1,7 -diamino-3 ,7-dimethyl-oc tanezqcHamcHzncHmHh 2H4 H2 1-amino-8-(3-aminopropylamino -p-menthane Theamines corresponding to Formula IV may be made by conventionalprocedures of monocyanoethylation or monocyanomethylation of tertiaryalkyl carbinamines having the formula duce the correspondingcyanoalkylamine having the formula R: R J--NH(CH1)-CN 1,. where m is 1or 2 and subsequently reducing the nitrile group by the conventionalprocedures to an amine thereby producing products having the generalformula where p is 1 or 2.

Other members of the class defined by Formula IV may be made by thereaction of alkylenechlorohydrines with an amine of Formula VII inconventional fashion and the subsequent conversion of the hydroxyl groupto an amine by standard procedures.

The amines of the structure of Formula V may be prepared when Y ismethylene by reacting an imine of the structure of'the general formulaCQCH,

in conventional fashion with ammonia or a primary amine, such as methylamine, in the presence of aluminum chloride to open up the ring and toproduce the corresponding diamine of Formula V. "The other diamines ofFormula V in which Y may be an alkylene group of 2 to 10 carbon atomsare prepared by treating an unsaturated alcohol of the general formulaC=Y--0H with hydrogen cyanide and sulfuric acid in conventional fashionto produce an amino-alcohol of the general formula This aminoalcohol issubsequently converted to a diamine by conventional procedure involvingconversion of the hydroxyl group to an amino group.

Any polymerized ester of an acid of the group consisting of those havingthe general formula CH2:C(R)COOR7 (VIII) 'in which the alkyl group ismethyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, t-butyl, amyl,hexyl, heptyl,

'octyl, decyl and dodecyl.

The polymer to be aminolyzed may be a homopolymer of the ester (FormulaVIII) or it may be a copolymer of one or more of such esters with one ormore other inversely proportional to the temperature.

monoethylenically unsaturated.polymerizable compounds, .zSllCh asacrylonitrile,' the vinylaaromatic'compounds,

more particularly the vinyl aromatic hydrocarbons (e. g. styrene,isopropenyl toluene, methyl styrene, the various dialkyl styrenes,etc.), the various substituted acrylonitriles (e. g. methacrylonitrile,ethacrylonitrile, phenylacrylonitrile, etc.), acrylamide and the varioussubstifrom-those-used in practicing the present invention and thevarious N-substituted alkacrylamides, for instance N-monoalkyl and-dialkyl acrylamides and methacrylamides, e. g., 'N-monomethyl, -ethyl,-propyl, -butyl, etcrand N-dimethyl, -ethyl, -propyl, -but'yl,' etc.,acrylamides and methacrylamides, N-dialkylaminoalkyl acrylaniides ormethacrylamides, such as N-dimethylarninoethylacrylamide, N-monoaryl and-diaryl acrylamides and alkacrylamidcs, e. g., N-monophenyl and-diphenyl acrylamides and methacrylamides, etc.), vinyl esters 0containing a single CH =C grouping.

Depending uponthe particular comonomer selected, the polymer obtainedmay be changed from water-soluble to oil-soluble, to alcohol-soluble orto any combina- 'tion of these solubilities.

A polymer of methyl acrylate, either a homopolymer or-a copolymer, isthe preferred polymeric starting material because of the ease andrapidity with which aminolysis may be effected with any of thepolyamines ofthe structure of Formulas IV, V, and VI hereinabove.

Generally, aminolysis is performed in a medium which is anhydrous orcontains but little water unless considerable carboxyl groups aredesired in the final polymeric product. The polyamine itself may serveas the solvent a 'as well as the reactant for aminolyzing the polymenzedmethyl acrylate and aminolysis maybe eflfected at temperatures of 90 to130 C. in a time of 96 hours to 24 hours respectively, the time requiredgenerally being In the presence of a 3-to-4-fold excess of polyamine,complete aminolysis may be effected in the times and the temperaturesjust mentioned, and it has been found that the higher the temperatureemployed, the higher is the final molecular weight of polymer obtained.A catalyst to accelerate the reaction is unnecessary, but-an alkoxide,

such as sodiumrnethoxide, sodium ethoxide, or the like,

may be used in amountsof from /2 to 2% by weight of the polymer. With acatalyst, an amount of the --polyamine equivalent to the ester groups tobe aminol-lyzedmaybe dissolved in a solvent such as toluene oradditional polyamine, either the same or. different, or an alcohol, suchas methanol, ethanol, or butanoL'and' the complete aminolysis may beobtained in eight hours at a. temperature of 80 to'"90 C. Anadvantageous sys- .tem is to start in toluene in which the polymerizedester is soluble and during the reaction to add an alcohol such .asmethanol, ethanol, or butanol in which the aminolyzed polymer. issoluble, and subsequently to remove the solvent to obtainthe' finalpolymer.

The polymeric esters of alcohols other than'methyl,

such as of ethyl alcohol, propyl alcohol, butyl alcohol,

and so on, require an increase in the time and tempera- .ture factor toproduce a corresponding conversion of .ester groups to amido groups inthe polymer. Generally, "when the polyamine used contains a primarynitrogen gatom, it is necessary to maintainthe reaction medium.-containing-the polymeric esterand polyamine at a tem-:peraturebeloW'l30. C. in order to avoid imide forma- .of thedinalpolymer. However, when the aminolysis. is

effected by an amine containing only secondary nitrogen atoms, there isno appreciable cross-linkingor imide formation even at highertemperatures upto 180 to ester groups without cross-linking. Generally,however,

the aminolysis may be effected at temperatures of 180 to 200 C. forthree to seven hours with production of uncrossed-linked products whichare up to aminolyzed. Generally toget a largerproportion of theestergroups or all thereof in the polymer aminolyzed, a 5.-toi0-fold excessof polyamine maybe reacted at a temperature of 130 C. for a time of fromfour to seven days. Alternatively, an alkoxide catalyst may be used with2-to-4-fold excess amine or an amount of polyamine equivalent to theester groups to be aminolyzed maybe used at 130 C.

As the alkyl group of the ester increases in size, more drasticconditions are necessary to effect aminolysis; thus, when polymerizedmethyl methacrylate is replaced with polymerized ethyl methacrylatelonger timesand higher temperatures must be used. As already stated,imide formation may be prevented by the use of polyaminesv which containonly secondary'nitrogen atoms.

The difference in reactivity of these various esters makes it possibleto obtain for all practical purposes a selective aminolysis ofcopolymers containing different ester units. For example, when the finallinear polymeric compound desired to be produced is one containtionwithrconsequent cross-linkingand insolubilization ing methylmethacrylate as cornonomer units, a copolyiner of methyL-acrylate andmethyl methacrylate in apso. that aminolysis converts the ester groupsof the methyl acrylate units to amide units without affecting the esterunits of the methyl methacrylate to any considerable extent. Such anaminolysis, for example, may be effected at to120 C. in the presence ofan amount of a polyamine which is equivalent to the ester groups in themethyl acrylate portion of the copolymer. Similarly, if it is desired toproduce acopolymer containing one or-more comonomers of non-ester typelisted above, such asof styrene, a corresponding copolymer, as .ofstyreneand methyl acrylate, may beusedasthe start .ing material in whichthe proportion of acrylateunits corresponds to the number of acrylamideunits desired and all such acrylate units may be converted to. amidegroups in the aminolysis. 1

The conventional procedure for making amides by reacting a halide, suchas the chloride, of the corresponding polymeric organic acid cannot beemployed to make the polyamides of the present invention because thepolyamine cross-links the polymer. Similarly'reaction of the polyaminewiththe chloride of the polymerizable acid in monomeric form produces adiamide or triamide which contains two or three ethylenicallyunsaturated points in the molecule and on polymerization, crosslinkingtakes place. It is both surprising and unexpected therefore that thepolyamines above react with the polymerized esters without.cross-linking them. The

aminolysis procedure of the present invention avoids the use of organicacid-chlorides which have lachrymatory properties and may often bedifficult or unpleasant to make or handle. While it practically alwaysleaves some free carboxyl groups in the aminolyzed polymers-unlessextreme care is taken to maintain strictly anhydrous conditions duringthe reaction, the carboxyl groups can be avoided whenanhydrousconditions are strictly maintained. However, it has been foundthat in practical 'operationswhere a small amount of water is present,theapolymeric product obtained by the-aminolysis step 7 contains from0.1 to 10 molar percent of carboxyl groups.

The properties of the copolymers depend on the character of the basicnitrogen groups and also on the properties and character of any othercomonomer or comonomers present in the product. Various solubilities areobtainable. For example, the polymer obtained by the aminolysis ofpolymerized methyl acrylate to the extent of at least of its estergroups with 1,2-diamino- 2-methyl propane can be neutralized with aninorganic acid, such as sulfuric or hydrochloric acid to produce awater-soluble salt. A similar polymer derived from polymerized methylmethacrylate requires at least 30% of the ester groups to be aminolyzedwith the same diamine in order to produce corresponding watersolubility.By providing long chain groups either on the nitrogen of the amide or ina comonomer with the amide units, oil solubility may be obtained.Generally all of the water-soluble and oil-soluble polymers are alsoalcohol-soluble except those having a large proportion of very longchains.

The new polymers and derivatives thereof are useful for many purposes.Thus, they serve as bactericides, fungicides; antistatic agents fortreatment of hydrophobic plastic materials such as cellulose esters,cellulose acetate, vinyl resins, etc. in form of fibers, filaments,films, yarns, fabrics; for absorption of acid ions from liquids, such asoils or aqueous solutions; for fiocculating suspended matter in aqueoussystems, as an aid in clarification and filtration thereof; asaggregating agents for conditioning soil to facilitate the growth ofplants, as dispersants, softening agents for cellulosic textiles orfilms, especially rayon, cellulose acetate, and cotton; as thickeners ofcoating compositions, such as latex or similar dispersions of polymers,especially of elastomeric type; as modifying components of film-formingmaterials, to improve the dyeing and resistance to gas-fading of fibers,filaments, films, textiles, and other shaped articles,

formed therefrom, particularly of cellulose acetate and acrylonitrilepolymers containing at least 75% acrylonitrile in the polymer molecule,especially when a common solvent, such as dimethylformamide ordimethylacet-' amide is used to prepare a spinning or extrusion dopecontaining the film-forming polymer and the dye-modifying polymer; asanchoring agents, especially for addition to paper pulp or cellulosicpulps on which they are selectively absorbed and to which they areadapted to anchor acidic materials, such as copolymers of acrylic ormethacrylic acid with other vinyl monomers as is described inMcLaughlin, Serial No. 410,450, filed February 15, 1954, now UnitedStates Patent 2,765,229; as a pharmaceutical, especially for fungicidaland bactericidal purposes; also to isolate protein fractions by formingan insoluble complex and regenerating the protein.

For use as non-phytotoxic bactericidal fungicides, the polymers of theinvention are preferably reacted with agents for quaternizing thenitrogen atoms. For this purpose, a preferred group of the compounds ofthe invention are those of controlled water-solubility which contain 30%to 70% of quaternary N-containing monomeric units in which the averagenumber of carbons on the monomeric units containing a quaternary groupare from 10 carbons to 40 carbons.

The N-aminoalkyl-polyacrylamides of the present invention undergonumerous reactions to give useful products difficult to obtain in otherways. For example, reaction of acetyl chloride with the product ofcomplete aminolysis of poly-(methylacrylate) byN-isopropylaminopropylamine (herein designated as polymer A) produces anamide derivative which forms tough, flexible coatings. Reaction of thispolymer A with stearoyl chloride produces an oil-soluble polymer whichdepresses the pour point of oils when added in amounts of /2 to 5% byweight. Reaction of CH SO C1 with polymer A produces sulfonamides havingfilm-forming properties.

Reaction of omeomaOsomr with polymer A produces a long-actingbacteriostatic polymeric sulfonamide. Alkylene diisocyanates, such asethylene diisocyanate, may be mixed with the polymers, such as polymerA, and reacted after extrusion, coating, casting, or other types ofshaping operation by baking with or without a catalyst, to producecross-linked, infusible materials of rubbery properties. Reaction withmonoisocyanates produces ureides which react with aldehydes, etc., suchas formaldehyde, to form infusible hard products. Reaction occurs withalkylene oxides, such as propylene oxide, ethylene oxide, and mixturesthereof. For example, reaction of polymer A with ethylene oxide produceswater-soluble surfactants having wetting, dispersing and/or emulsifyingproperties. Reaction with cyanogen chloride produces cyanamides.Cross-linked polymers are also obtained by reacting the polymers, suchas polymer A, with aldehydes, especially formaldehyde and acetaldehyde.Reaction of the polymers including polymer A with (C H O) POCl producesderivatives having in all cases a reduced suspectibility to fire and inmany cases a material that is capable of fireproofing inflammablearticles, when incorporated therein or coated thereon in properproportions.

The new polymers of the invention may be compounded with dyes, pigments,mold lubricants, fillers, plasticizers and other resinous materials andshaped by conventional molding techniques, such as compression molding,injection molding, casting, extrusion, etc., into articles of any shapedesired, including rods, tubes, bars and so on. Examples of other resinsthat may be incorporated include thermoplastic vinyl and acrylic typesof polymers, polyamides of the nylon type, polyesters, such aspolyethylene terephthalate, polyethylene, thermosetting reactionproducts, such as those of the phenol-formaldehyde, urea-formaldehyde,melamineformaldehyde, thiourea-formaldehyde types, and the polyepoxideresins. For example, a mixture of a polymer of the present inventionwith an epoxide-containing polymer, especially a polymer of glycidylacrylate, in relative amounts of each from 5 to and vice versa is usefulas a coating, casting, or molding composition. Even a small amount ofeither component cross-links the other component to form insoluble,infusible, thermoset products.

The following examples are illustrative of the invention:

Example 1 (a) There is charged into a reaction vessel 43 g. /2 mole) ofa homopolymer of methyl acrylate (whose 50% solution in toluene at 25 C.had a Gardner-Holdt viscosity of 24+ (ca. 75 poises)) and 116 g. of3-isopropylaminopropylamine. The mixture is heated 4 days at C. Thesolution is then diluted with methanol (300 ml.) and passed through acolumn of an ion-exchange resin in the acid form to absorb excessunreacted amine but not the polymer. The solution is stripped by heatingat 100 C. for about 8 hours under vacuum to an ultimate pressure of /2mm. of Hg. absolute. The solid product obtained amounted to 67 g. andcontained 14.3% nitrogen which corresponds to 88% aminolysis. It issoluble in water, methanol, ethanol, and dimethylformarnide.

The product has bactericidal and fungicidal properties. When added to asolution in dimethylformamide of a copolymer containing about 90%acrylonitrile and 10% methylacrylate, in an amount of 5% to 10% on theweight of the acrylonitrile polymer, fibers and other articles extrudedor otherwise formed from the solution have improved dyeability,particularly with acid dyes.

' (b) The product of' part (a) hereof is dissolved in dimethylformamidecontaining one mole of pyridine per mole of basic nitrogen in thepolymer. Then diethyl chlorophosphate in theamount of one mole'per moleof basic nitrogen is added to the solutionand the mixture is heated to2030 C. for eight hours. The resultant solution of polymericamidophosphate is separated from the pyridine hydrochloride and thepolymer maybe isolated by precipitation with petroleum ether. Thepolymer is dissolved in methanol to form a solution which is applied, asby padding, to a cotton fabric. 0n drying, the fabric hasreduced'fiammability and retains a'soft handle.

Example 2 There is charged into a reaction vessel 86 g. ofpolymerizedmethyl acrylate:'(having a viscosity at 25 C. of 75 poises asa 20% solution -in ethyl acetate) and 130 grams of3-(t-butylarnino)propylamine to which is added 260 g. ofdimethylformamide. The solution is heated at 128 C. for 48 hours. Thevolatiles are removed by heating in vacuum and the residue is dissolvedExample 3 The procedure of Example 1(b) is followed except that thechlorophosphate is replaced with stearoyl chloride and the solution isheated at 80 C. for about 12 hours. The polymer in the resultingsolution is precipitated by pouring it into water. The polymer is thendissolved in benzene and added to hydrocarbon oils in amounts of about/2 to 5% of polymer on the weight of the oil. The resulting lubricatingoils have their pourpoint depressed by the added polymer and haveimproved detersive properties.

Example 4 The procedure of Example 1(a) is followed except that themethyl polyacrylate was replaced by the same amount of a copolymer of 30mole percent of methyl acrylate and 70 mole percent of2-ethylhexylacrylate and the diamine was replaced by the same amount of1,2-diamino-2-methyl-propane. The resulting polymer contained about 28mole percent of amide groups or units which are believed to havereplaced the methyl acrylate groups preferentially. The product isinsoluble in water, but soluble in benzene.

(b) The product (one mole) of part (a) hereof is dissolved indimethylformamide and .sufiicient ethylene oxide is added to give aproduct with a cloud-point of about 60 C. when a 1% solution thereof inWater is gradually heated. This required approximately 16 moles ofethylene oxide per mole of basic nitrogen. The resulting material is agood detergent, dispersing agent and emulsifier.

Example 5 (a) A mixture of methyl polyacrylate (3 moles) with the.mixture is heated r050. i Cxfor '4 hours to complete the reaction. Thepolymercomprising the'following-zunits [-o-m-cnq CH2- H 7 on IQLNCONHCaH:

CHr-CH in the dimethylformamide solution'is 'c'oated on surfaces ofmetal, glass, wood, and so on and subsequently baked at 150 C. for 10minutes. Itfigives "tough, flexible thermoplastic films.

(b) To a second portion of the polymer solutionrformaldehyde (20% byweight of the polymer) and butyl acid phthalate (4% by weight of thepolymer) are added. The mixture is coated on panels of metal, wood, andglass and baked at 150 C. for ten minutes. The resulting coating istough, flexible, but is thermoset and insoluble in organic solvents.

"Example 6 The procedure of Example 1(a) is followed except that thepolyaminev is replaced by t-butylaminopentyl amine. Anoil-soluble.pol-yamide is obtained.

Example 7 The procedure of Example 2 is followed except that thepolyamine is replaced by isopropylaminodecylamine.

Example 8 The procedure of Example2 is followed except that thepolymerized ester is replaced by a copolymer of 30 mole percent ofmethyl acrylate and 70 mole percent of lauryl methacrylate and thepolyamine used is (benzyldimethyl)methylaminohexylamine. The productisoilsoluble and the addition of 1% by weight thereof to a lubricatingoil served effectively as a pour-point depressing agent.

Example 9 The procedure of Example 8 is followed except that thepolyamine is replaced by (heneicosyldimethyl)methylaminoethoxyethoxyethylarnine. The product obtained had of itsmethylacrylate ester groups aminolyzed and is an efficient pour-pointdepressant in oils.

Example 10 (a) The procedure of Example 8 is followed except that thepolyamine is replaced by (p-methoxyphenyldb methyl)-methylaminopropylamine.

Aminolysis products in which the methyl acrylate units are substantiallycompletely aminolyzed are similarly obtained when this polyamine isreplaced by:

Tris-(hydroxymethyl)methylaminopropylamine,t-Butylaminopropoxypropylarnine,(w-Hydroxydecyldimethyl)methylaminopropylamine,1,7-diamino-3,7-dimethyl-octane, and

1-amino-8- 3 -aminopropylamino) -p-menthane.

(b) The several products obtained in part (a) hereof are reacted with 20moles of ethylene oxide per mole of basic nitrogen in the respectivecopolymers. The resulting products are surface active detergents.

It is to be understood that changes and variations may be made Withoutdeparting from the spirit and scope of the invention as defined in theappended claims.

We claim:

1. A composition of matter comprising a linear poly mer the main chainof which consists entirely of carbon atoms, said polymer being acopolymer of zero to about 52 mol percent of methyl acrylate, 0.1 to 10mol percent of acrylic acid, and at least 48 mol percent of 1 1 amideunits selected from the group consisting of those of the generalFormulas I and II following:

2. A composition as defined in claim 1 in which the amide nitrogencarries a 3-(isopropylamino)propyl substituent.

3. A composition as defined in claim 1 in which the amide nitrogencarriesv a 3-(t-butylamino)propyl substituent.

4. A composition as defined in claim 1 in which the amide nitrogencarries a 1,2-diamino-2-methyl-propyl substituent.

5. A composition as defined in claim 1 in which the amide nitrogencarries an isopropylaminodecyl substituent.

6. As a composition of matter, a linear polymer containing in thepolymer about 48 to about 100 mol percent of N-3-(t-butylamino)propylacrylamide units, 0.1 to 10 mol percent of acrylic acid units, and about0 to about 52 mol percent of methyl acrylate units, the main chain ofsaid polymer consisting entirely of carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS2,146,210 Graves Feb. 7, 1939 2,311,548 Jacobson et a1. Feb. 16, 19432,643,958 Kleiner et a1. June 30, 1953 2,675,359 Schneider Apr. 13, 1954FOREIGN PATENTS 655,951 Germany Jan. 27, 1938

1. A COMPOSITION OF MATTER COMPRISING A LINEAR POLYMER THE MAIN CHAIN OFWHICH CONSISTS ENTIRELY OF CARBON ATOMS, SAID POLYMER BEING A COPOLYMEROF ZERO TO ABOUT 52 MOL PERCENT OF METHYL ACRYLATE, 0.1 TO 10 MOLPERCENT OF ACRYLIC ACID, AND AT LEAST 48 MOL PERCENT OF AMIDE UNITSSELECTED FROM THE GROUP CONSISTING OF THOSE OF THE GENERAL FORMULAS IAND II FOLLOWING: